Novel contaminants identified in fish kills in the Red River watershed, 2011-2013.

Provisional molecular weights and chemical formulas were assigned to 4 significant previously unidentified contaminants present during active fish kills in the Red River region of Oklahoma. The provisional identifications of these contaminants were determined using high-resolution liquid chromatography-time-of-flight mass spectrometry (LC-TOFMS), LC-Fourier transform ion cyclotron resonance mass spectrometry (LC-FTICRMS), and LC-ion trap mass spectrometry (LC-ITMS). Environmental water samples were extracted using a solid-phase extraction (SPE) method, and sediment samples were extracted using a modified sonication liquid extraction method. During screening of the samples, 2 major unknown chromatographic peaks were detected at m/z 624.3 and m/z 639.3. The peak at m/z 639.3 was firmly identified, through the use of an authentic standard, as a porphyrin, specifically chlorin-e6-trimethyl ester, with m/z 639.31735 (M + H)+ and molecular formula C37 H43 N4 O6 . The other major peak, at m/z 624.3 (M + H)+ , was identified as an amide-containing porphyrin. It was discovered that the amide compound was an artifact created during the SPE process by reaction of ammonium hydroxide at 1 of 3 potential reaction sites on chlorin-e6-trimethyl ester. Other unique nontargeted chemicals were also detected and the importance of their identification is discussed. Environ Toxicol Chem 2018;37:336-344. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Sampling for silver nanoparticles in aqueous media using a rotating disk electrode: evidence for selective sampling of silver nanoparticles in the presence of ionic silver.

Amendment of a carbon paste electrode consisting of graphite and Nujol®, with a variety of organic and inorganic materials, allows direct adsorption of silver nanoparticles (AgNPs) from aqueous solution in either open or close circuit modes. The adsorbed AgNPs are detected by stripping voltammetry. Detection limits of less than 1 ppb Ag are achievable with a rotating disk system. More than one silver peak was apparent in many of the stripping voltammograms. The appearance of multiple peaks could be due to different species of silver formed upon stripping or variation in the state of aggregation or size of nanoparticles. With most of these packing materials, dissolved Ag+ was also extracted from aqueous solution, but, with a packing material made with Fe(II,III) oxide nanoparticles, only AgNPs were extracted. Therefore, it is the best candidate for determination of metallic AgNPs in aqueous environmental samples without interference from Ag+.